Dyestuffs and processes for their production and use

ABSTRACT

Dyestuffs of the formula   WHEREIN F is a radical of an organic dyestuff, W is a bridge member, X and Y are halogen atoms, arylthio, or aryloxy, and m is an integer. These dyestuffs are particularly suitable for dyeing textile materials containing nitrogen or hydroxyl groups, i.e., cellulose, wool, silk, synthetic polyamide, and polyurethane.

United States Patent Schundehutte et al.

DYESTUFFS AND PROCESSES FOR THEIR PRODUCTION AND USE Inventors: Karl-Heinz Schundehutte; Kersten Trautner, both of Farbenfabriken Bayer AG, Cologne, Stemmheim, Germany Filed: June 1, 1971 Appl. No.: 148,927

Related US. Application Data Continuation of Ser. No. 810,889, Jan. 16, 1969, abandoned, which is a division of Ser. No. 517,424, Dec. 29, 1965, Pat. 3,480,641, which is a division of Ser. No. 469,907, July 6, 1965, abandoned.

US. Cl ..260/303 Int. Cl. ..C07d 91/32 Field of Search ..260/303 51 Aug. 29, 1972 [5 6] References Cited UNITED STATES PATENTS 3,480,641 11/1969 Schundehutte et al. ...260/303 Primary ExaminerAlex Mazel Assistant Examiner-R. J. Gallagher AttorneyPlumley, Tyner & Sandt [57] ABSTRACT Dyestuffs of the formula 1 J X-C-CO O-W1F ll lLY 6 Claims, No Drawings DYESTUFFS AND PROCESSES FOR THEIR PRODUCTION AND USE This application is a continuation of application Ser. No. 810,889, filed Jan. 16, 1969, now abandoned, which in turn is a division of Ser. No. 517,424, filed Dec. 29, 1965, now US. Pat. No. 3,480,641, which in turn is a division of Ser. No. 469,907, filed July 6, 1965, now abandoned.

The present invention relates to new valuable dyestuffs of the general formula XCCC O-W F l (LY J In this formula, F denotes the radical of an organic dyestuff, W is a bridge member, X and Y are halogen atoms, arylthio groups or aryloxy groups, and m is an integer.

The dyestuffs can belong to various classes, for example, to the series of metal-free r metal-containing monoor polyazo dyestuffs, metal-free or metal-containing azaporphin dyestuffs, preferably phthalocyanine dyestuffs, anthraquinone, oxazine, dioxazine, triphenylmethane, nitro, azomethine, benzathrone, and dibenzathrone dyestuffs and of polycyclic condensations compounds of anthraquinone, benzathrone, and dibenzathrone compounds.

In the dyestuffs of the general Formula (I), the radical is linked with the dyestuff molecule via any bridge member. The Nl-I-- group is of special interest as a bridge member. However, the carboxyl group can also be linked to, for example, a secondary amino group or an amide group, e.g., a sulphonamide or carbonamide, aminotriazine or aminodiazine group. The amino group can, in turn, be linked to the basicdyestuff molecule, i.e., to an aromatic nucleus of the dyestuff molecule, directly or via an alkylene, aralkylene, or arylene group. If the bridge members W contain heterocyclic ring systems, such as triazinylamino and pyrimidinylamino radicals, these may also contain reactive halogen atoms.

The preferred bridge member, W, may be represented by the following group:

wherein the N atom is bonded to the CO- group of the isothiazolyl radical; R is lower alkyl or lower alkyl substituted with OH, and n is 1 or 1.

The preferred reactive substituents X and Y in the isothiazole radical are halogens, such as chlorine and bromine.

Dependent upon the type of their substituents, the new dyestuffs of the Formula (I) can be water-soluble as well as barely soluble or insoluble in water. The radical F may contain the substituents customary for the dyestuffs concerned, such as sulphonic acid, carboxylic acid, possibly substituted sulphonamide, sulphone, alkylamino-aralkylamino, arylamino, acylamino, nitro, cyano, halogen, hydroxyl, alkoxy, thioether, azo groupings and the like. The dyestuffs may, moreover, contain groupings capable of fixation, such as monoor dihalo-triazinylamino, mono-, di-or trihalopyrimidinylamino, 2,3-dihalo-quinoxaline-6-carbonylor -6- sulphonylamino, l,4-dihalo-phthalazine--carbonylor -6-sulphonylamino, 2-halobenzothiazole-S-carbonyl-or -5-sulphonylamino, esterfied sulphonic acid alkoxyamide and alkoxysulphone groups, sulphofluoride, haloalkylamino, acryloylamino, haloacylamino groups and the like.

The new dyestuffs can be synthesized by various methods. For example, dyestuffs or primary dyestuff products ,which contain amino or amide groups and have a reactive hydrogen atom at the amino or amide nitrogen, can be reacted with compounds of the general formula in which X and Y have the meaning given above and halogen stands for a halogen atom, preferably chlorine, and in the case where primary dyestuff products are used, these can be transformed in a suitable manner into the desired end dyestuffs.

Dependent upon the number of reactive groupings in the dyestuff radical or in the dyestuff intermediates, which are suitable for the conversion, one or more groupings of the Formula (II) can be incorporated with the dyestuffs. In most cases, the number m will not exceed 4, but it is also possible to synthesize dyestuffs, especially those of a higher molecular structure, with more than 4, e.g., up to 8, groupings of the Formula (II).

The intermediate products of the Formula (III) are in part known from the literature (cf. e.g., J. Org. Chem. 29, 660 [1964]).

Among the great number of dyestuffs obtainable according to the present process those products are especially easily accessible which are derived from amino group-containing azo dyestuffs of the benzene-azobenzene, benzene-azomaphthalene, naphthalene-azonaphthalene, benzene-azo-aminopyrazole and pyrazolone series and from the hetero-azo-aryl series and the aminoanthraquinone series with nuclear-positioned and/or externally linked amino groups, by reaction with compounds of the Formula (III).

, The new reactive dyestuffs can be produced not only by starting from the finished dyestufis; it is also possible to react suitable coupling components which contain amino or amide groups and have at least one reactive hydrogen atom at the amino or amide group, with compounds of the Formula (Ill) to form preliminary products which are then coupled with suitable diazonium compounds. Inversely, diazonium compounds which contain reactive radicals of the Formula (II) can be coupled with suitable azo components to produce the azo dyestuffs (I) to be obtained according to the present process.

(III) The new dyestuffs are extremely valuable products which are suitable for various purposes of application. The waterssoluble compounds are of special interest for the dyeing of textile materials containing nitrogen or hydroxyl groups, especially of textile materials of native and regenerated cellulose, further, of wool, silk, synthetic polyamide and polyurethane fibers. Due to the reactive substituents X or Y in the isothiazole radical, the products are particularly well suited as reactive dyestuffs for dyeing cellulose materials by the methods recently disclosed for this purpose. The fastness properties attained, especially the fastness to wet processing, are excellent.

For dyeing cellulose, the dyestuffs are 191 used in an aqueous solution to which compounds of alkaline reaction such as alkali metal hydroxide or alkali metal carbonate, or compounds convertible into substances of alkaline reaction, such as alkali metal bicarbonate, may be added. Further adjuvants can be added to the solution, provided they do not react with the dyestuffs in an undesirable manner. Such additives are, for example, surface-active substances, such as alkylsulphates, or compounds preventing migration of the dyestuff, or dyeing assistants such as urea (for improving the solubility and fixation of the dyestuffs), or inert thickeners such as oil-in-water emulsions, tragacanth, starch, a1- ginate, or methyl cellulose.

The solutions or pastes thus prepared are applied to the material to be dyed, for example, by padding on the foulard (short bath) or by printing, and subsequently heated for some time at an elevated temperature, preferably at 40l50C. Heating can be performed in the hotflue, in a steaming apparatus, on heated rollers or by introducing the material into heated concentrated salt baths, using these methods singly or in any sequence.

When a padding liquor or dyebath without alkali is used, the dry material is subsequently passed through a solution of alkaline reaction to which sodium chloride .or Glaubers salt is added. The addition of salt reduces the migration of the dyestuff from the fiber.

The material also be pretreated with one of the aforesaid acid-binding agents, subsequently treated with the solution or paste of the dyestuff, and, finally, fixed at an elevated temperature as described above.

In the so-called cold-batch padding process, the subsequent heating of the padded fabric can be saved by storing the fabric for some time at room temperature.

In this process, sodium carbonate is preferably used as alkali.

For printing materials containing hydroxyl groups, a printing paste is used which consists of the dyestuff solution, a thickening agent such as sodium alginate, and a compound of alkaline reaction or splitting off alkali when heated, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium bicarbonate, and the printed material is rinsed and finally soaped, if desired.

If the dyestuffs contain groupings which form metal complexes, the fastness properties of the dyeings and prints can frequently be improved by an after-treatment with metal-yielding agents, such as copper salts, e.g., copper sulphate, chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

Textile materials which contain amide groups, such as wool, silk, synthetic polyamide and polyurethane fibers, are generally dyed by the methods customary for this purpose in an acid to neutral medium; a final raising of the pH value of the dyebath, for example, to a pH of 6.5-8.5 being sometimes of advantage.

The dyestuffs are applied to a synthetic polyamide fabric, for example, as solutions, or, preferably, in the dispersed form and subsequently after-treated, possibly together with preferably small amounts of acid-binding agents, such as sodium carbonate. Especially advantageous results are achieved with those dyestuffs which are insoluble or only barely soluble in water. These are worked up by known methods with the addition of the known assistants into a dyestuff dispersion and applied as such in the dyebath and/or padding liquor, or in a printing paste. The assistants suitable for this application are, inter alia, compounds which prevent the migration of the dyestuff on the fiber, such as cellulose ethers, alkali metal chlorides and sulphates; wetting agents, such as condensation products from ethylene oxide and fatty alcohols or phenols, sulphonated fatty alcohols; solvents, such as thiodiglycol; and thickening agents, such as starch, tragacanth, alginate thickening, gum arabic, etc.

The after-treatment of the dyeings, impregnations and prints obtained on fabrics of polyamide fibers is carried out, preferably, at a temperature of 50-1l0C for a period of 5-60 minutes. Also in this case the fastness properties of the dyeings can sometimes be improved with metal-yielding agents, such as copper salts, e.g., copper sulphate, or chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate, provided that the dyestuffs employed contain groupings forming metal complexes.

The dyeings and prints obtainable with the new dyestuffs are generally distinguished by good to very good fastness properties, especially by excellent fastness to wet processing.

The following examples are given for the purpose of illustrating the invention, and unless otherwise noted, all parts are by weight.

EXAMPLE 1 To a solution of 34.7 parts of 2-aminonaphthalene- 4,8-disulphonic acid sodium salt and seven parts of sodium nitrate in 300 parts of water, are added while cooling with ice, 28 parts by volume of concentrated hydrochloric acid, and the mixture is stirred at 0-10C for 30 minutes. After removing the excess nitrous acid, 10.7 parts of 3-aminotoluene dissolved in 10 parts by volume of concentrated hydrochloric acid and parts of water are added and the coupling is completed by neutralizing the mixture to a pH of 3-5. The resultant aminoazo dyestuff is salted out, filtered off with suction, washed and then dissolved again at a pH of 7 in 700 parts of water with the addition of a sodium hydroxide solution. The aqueous solution is then mixed with 21.6 parts of 3,5-dichloro-l,2-isothiazole-4-carboxylic acid chloride (b.p., 102C/8 mm Hg) dissolved in 50 parts of acetone and vigorously stirred. By the reaction which sets in, the mixture is spontaneously heated to 3540C', the liberated hydrochloric acid is neutralized with a sodium carbonate solution, until free amino groups can no longer be detected. The resultant dyestuff of the formula is salted out with 80 parts of sodium chloride, pressed off, washed, and dried at 40-50C in a vacuum. It is a yellow powder which dissolves in water with a yellow color.

When a cellulose fabric is printed with a printing paste which contains, per kilogram, 15 g of the dyestuff, 100 g of urea, 300 ml of water, 500 g of alginate thickening (60 g of sodium alginate per kg of thickening), 2 g of sodium hydroxide and g of sodium carbonate, and which has been made up with water to l kilogram, followed by drying, steaming at 150C for 8 minutes, rinsing with hot water and boiling with soap, an intense reddish-yellow print of good fastness to washing and light is obtained.

EXAMPLE 2 0.1 mol of the copper complex compound of the formula Naoas 803N3- Na 03S OCu (prepared according to the instructions of German Patent Specification No. 1,117,235 by coupling diazotized l-amino-8[benzene-sulphonyloxy1- naphthalene-disulphonic acid-[3,6] in a soda-alkaline medium with the equivalent amount of 2-acetylamino- 5-hydroxynaphthalene-disulphonic acid-[4,8], conversion of the monoazo compound into the copper complex by oxidative coppering and hydrolysis of the acetyl and benzene-sulphonyl groups), is dissolved in 2,500 parts by volume of water at 35C at a pH of 6-6.5 and mixed at this temperature with a solution of 0.1 mol of 3,5-dichloro-l,2-isothazole-4-carboxylic acid chloride in 50 ml of acetone. During condensation of pH of 66.5 is maintained by the addition of a sodium carbonate solution. When the reaction is completed, the dyestuff is salted out and isolated. After drying, the dyestuff is a dark powder which dissolves in water with a blue color.

One hundred parts by weight of a cotton fabric are padded on the foulard at room temperature with an aqueous solution containing 2 percent of the dyestuff, g/liter of sodium hydrogen carbonate and 150 g/liter of urea, dried intermediately, heated at'l40C for 10 minutes, then rinsed and boiled with soap. The fabric is dyed in very clear blue shades fast to wet processing.

EXAMPLE 3 In 300 parts of water at 50C are dissolved at a pH of 7-8, 46 parts of the dyestuff obtained by coupling diazotized 2-aminonaphthalene-4,8-disulphonic acid with 3-methylamino-toluene following the procedure of Example 1, and mixed in the presence of excess sodium acetate or calcium carbonate at 3540C portionwise with a total of 31 parts of 3,5-dichloro-l ,2- isothiazole-4-carboxylic acid chloride, and stirred at the same temperature, until a sample no longer shows a change of color when acid is added. The resultant dyestuff of the formula SIOsNa at -Q- -w C CH: I Cl S no- 59 .182.,

is salted out, filtered off with suction, washed and dried.

A cotton fabric is impregnated with a solution at 2025C, which contains, per liter of liquor, 20 g of the above dyestuff and 0.5 g of a non-ionic wetting agent (e.g. a polyethoxylated oleyl alcohol) as well as 150 g of urea and 15 g of sodium bicarbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about percent. After an intermediate drying at 5060C, the material is heated at C for 10 minutes, and the dyeing thus obtained is thoroughly rinsed with hot water and treated at the boil for 20 minutes with a solution containing, per liter, 5 g of Marseilles soap and 2 g of sodium carbonate. After rinsing and drying, an intense reddish-yellow dyeing of good fastness to wet processing, rubbing and light is obtained.

In the following table the diazo components and the coupling components having linked thereto through the amino group the reactive component 3,5-dichlorol,2-isothiazole-4-carboxylic acid chloride are listed, from which dyestuffs can be synthesized following the procedure given in Examples 1-3; the shades obtained by one of the methods of application described above are also stated in the table.

Into a solution of 36.5 parts of the sodium salt of lamino-8-hydroxynaphtahlene-3,6-disulphonic acid in 100 parts of water are introduced with good stirring, 21.6 parts of 3,5-dichloro-l,2-isothiazole-4-carboxylic acid chloride, and the mixture is stirred at 20-40C, while continuously neutralizing the liberated hydrochloric acid to a pH of 6'/, until free amino groups can no longer be detected. The dyestuff intermediate thus obtained is coupled, after diluting it with 600 parts of water and adding 12 parts of sodium carbonate, at 5l0C with 17.5 parts of diazotized 2- aminobenzene-sulphonic acid dissolved in 200 parts of water. The dyestufi formed at a final pH of about 7 and having the formula is salted out with 100 parts of sodium chloride, filtered off with suction, washed and dried at 4050C in a vacuum. The dyestuff forms small red needles which have a metallic luster and which readily dissolve in water with a red color.

When a fabric of cotton or regenerated cellulose is dyed or printed with this dyestufi by one of the methods described in Examples 1-3, clear bluish-red dyeings and prints of good fastness to wet processing, rubbing, and light are obtained.

Equally good results are obtained by the following process:

Fifty grams of cotton skein are dyed in 1 liter of a dyebath containing 1.5 g of the above dyestuff by raising the temperature from 20C to about 40C within 30 minutes while adding a total of 50 g of sodium carbonate and treating at the same temperature for 60 minutes. After rinsing, boiling with soap and drying, a bluish-red dyeing of good fastness to wet processing, rubbing, and light is obtained.

In the following table the shades of further dyestuffs are listed, which can be synthesized from the likewise mentioned diazo components and coupling components having linked thereto through the amino group the reactive component of the foregoing example, in analogy with the instructions of Example 12 or also by reaction of the corresponding aminoazo dyestuffs with the reactive component, and which can be dyed or printed on cellulose materials by one of the methods described above.

Ex. Diazo Coupling No. component component Shade 13 l-aminobenzene-2- l-( 3 '-aminobenzoylred sulphonic acid amino)-8-hydroxylnaphthalene-3,6- disulphonic acid 14 l-amino-2-carbuxyl-arnino-8-hydroxyred benzene-4-sulphonic naphthalene-3,6- acid disulphonic acid 15 l-amino-4-methyL l-amino-8-hydroxyred benzene-2-sulphonic naphthalene-3,6- acid disulphonic acid 16 lamino-3- (2'-[4"- l-amino-S-hydroxyred sulphophenylaminoI- naphthalene-3,6- 4'-chlorotriazinedisulphonic acid l',3,5'-yl-6')- aminobenzene-fisulphonic acid l7 -l--aminobenzene-2- Lamino-S-hydroxyorange sulphonic acid naphthalene-7 sulphonic acid 18 l-amino-3-(2-[4"- 2--amino-5-hydroxyorange sulphophenylaminolnaphthalenel7- 4'-methylamino sulphonic acid triazine-l ,3, 5- yl-6)-aminobcnzene- 6-sulponic acid 19 l-aminobenzene-Z- Z-methylamino-S- orange sulphonic acid hydroxy-naphthalene- 7-sulphonic acid 20 l-amino-4acetyl 2-methylamino5- scarlet amino-fi-sulphonic hydroxy-naphthaleneacid l-amin0-4-acetylamino-fi-sulphonic acid 21 scarlet EXAMPLE 22 Into a solution of 21 parts of the sodium salt of 1,3- diaminobenzene--sulphonic acid in parts of water, are introduced with good stirring 21.6 parts of finely powdered 3,5-dichloro-l,2-isothiazole-4carbox ylic acid chloride, and the mixture is stirred at 2()-4() C, while continuously neutralizing thc liberated hydrochloric acid to a pH of 6-7, until 11 sample, when diazotized and coupled with l-hydroxy-naphthalene-4- sulphonic acid, gives a clear yellowish-red coloration. The dyestuff intermediate formed is directly diazotized, after the addition of ice, with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and subsequently combined with a previously prepared solution of 47 parts of the sodium salt of lbenzoylamino-8-hydroxy-naphthalene-3,6-disulphonic acid and 12 parts of sodium carbonate in 200 parts of water, whereupon coupling takes place and the dyestuff of the formula is formed, which is salted blue filtered off with suction, washed and dried at 4050C in a vacuum. The dyestuff readily dissolves pH of water with a red color and amino groups bluish-red dyeings and prints on cellulose materials by one of the methods described above.

In the following table, there are listed the shades and the pH value of the coupling medium of dyestuffs which are produced in analogy with the instructions of Example 22 from a coupling component and a diazo component containing a further, preferably acylatable, amino group, and linked with the reactive component of the foregoing example through an amino group. The methods mentioned above can be used for dyeing and printing cellulose materials with the dyestuffs of the table.

hydroxy-triazin- HllDSl OHl l',3',5'-yl- 6'-amino)-8 hydroxy-naphthalene-3,6-disulphonic acid l-(3',5-dichloro-l '-2- thiazole-4'- carbonamido)-8- hydroxynaphthalene-3,6-disulphonic acid 2-hydroxy-naph- 8 thalene 3,6-disulphonic acid l-(3'-sulpho- 6 phenyl)-3-methylpyrazolone-S l-2',5'-dichloro-4-sulphophenyl)-3-methylpyrazolone-S l(5,7'-di 6 sulpho-naphthyl- 2'-)-3-methylpyrazolone-S 2-amino-8- hydroxynaphthalene-6- sulphonic acid 2- -acctylamino- 6-7 S-hydroxynaphthalene-7- sulphonic acid 28 l,3-diaminobenzene- 7 8 red -4-sulphonic acid scarlet yellow yellow 32 yellow l ,4-diaminobenzene 44.5 red 3-sulphonic acid 34 scarlet EXAMPLE 35 In 1,500 parts of water are dissolved at a pH of 7, 51.6 parts of the dyestuff of the formula NaO S NHZ obtained by diazotization of l-hydroxy-2- 0 Cu (I) NaOaS NH-0co0 01 ll ll 0 soaNa is salted out, pressed off, washed and dried at 4050C in a vacuum. Fabrics of cellulose materials can be dyed with this dyestuff by one of the methods mentioned above in ruby shades fast to wet processing, rubbing and light.

In the following table there are listed the heavy metal complexes of further aminoazo dyestuffs linked with the reactive component of the foregoing example through the amino group as well as the shades of these dyestuffs on cellulose materials. The production of the aminoazo dyestuffs and their metal complexes and the reaction of the latter with the reactive components can be carried out in analogy with the instructions of Example 35.

Ex. Complex-linked No. Aminoazo dystuff heavy metal Shade 36 l-hydroxy-2-aminobenzene- 4,6- Cu ruby disulphonic acid 2-amino 5-hydroxy-naphthalene-7 sulphonic acid 37 l-hydroxy-2-aminobenzene 4- Cu ruby sulphonic acid 2ethylamino- 5-hydroxy-naphthalene-7- sulphonic acid 38 l-amino-2-hydroxy-6 nitro Cu ruby naphthalenc-4-sulphonic acid 2-amino-5-hydroxynaphthalene-7-sulphonic acid 39 Cr greenishy 40 l-amino2-hydroxy-5- methyl Cu violet sulphonyl-benzene l-amino- 8-hydroxynaphthalene-3,6- disulphonic acid 4l Co grey 42 Cr 43 l-aminoQ-methylbenzene- 4- Cr greenish sulphonic acid l-amino-2- black hydroxy-S -mcthylbenzene 1-amino-8-hydroxy-naphthalene 4,6-disulphonic acid 44 (l-amino-Z- chlorobcnzene4- Cu navy sulphonic acid l-hydroxyblue 2- -acetylaminobenzene), saponified, 1 -amino-8-hydroxy-naphthalene- 3,6-disulphonic acid 45 C. grey 46 l-amino-S-hydroxynaphthalene-4- Co black sulphonic acid l-hydroxy 2,6-diaminobenzene-4-sulphonic acid 1,3-dihydroxybenzene 47 l-amino-8-hyd roxynaphthalene- Co black 3,6-disulphonic acid lhydroxy-2,6-diaminobcnzene-4 sulphonic acid Z-hydroxyhthalene 48 l-amino-8- hydroxynaphthaIene-4- Co black sulphonic acid l-hydroxy 2,6diaminobenzene-4-sulphonic acid 3-methyl-pyrazolone-(5) EXAMPLE 49 the copper-phthalocyanine-tetrasulphochl0ride freshly prepared in the usual manner by the action of chlorosulphonic acid and thionyl chloride on copperphthalocyanine, or of the isomeric copper-phthalocyanine-tetrasulphochloride synthesized from 1- sulphobenzene-3,4-dicarboxylic acid via the corresponding copper-phthalocyanine-tetrasulphonic acid, 96 parts (referred to 100 percent goods), is suspended in the form of the moist, thoroughly washed suction filter cake in 500 parts of water and 500 parts of ice, a solution of 50 parts of the sodium salt of 1,3- diaminobenzene-4-sulphonic acid in 500 parts of water is added and the pH value is adjusted to 8.5 with sodium carbonate. The suspension is stirred at room temperature for 24 hours, a pH value of 8.5 being constantly maintained by the continuous addition of sodium carbonate. The resultant condensation product is precipitated at a pH of 1-2 by the addition of sodium chloride, filtered off with suction, washed and then redissolved neutral in 1,000 parts of water. A solution of 65 parts of 3,5-dichloro-l ,2-isothiazole-4-carboxylic acid chloride in 100 parts acetone acetone is added dropwise with intense stirring to the blue solution, and the mixture is stirred at 3040C, while continuously neutralizing the liberated hydrochloric acid to a pH of 5-7, until free amino groups can no longer be detected. The reactive dyestuff of the formula s )n Cu-phthalocyanlne l Cl S (SOzHN thus obtained is salted out, washed and dried at 3040 C in a vacuum. It is a dark blue powder which dissolves in water with a blue color and dyes cotton and regenerated cellulose by one of the dyeing or printing methods mentioned above, in clear blue shades of good fastness to wet processing, rubbing, and light.

Instead of 96 parts of copper-phthalocyaninetetrasulphochloride, there can also be used 87 parts (referred to 100 percent goods) of the copperor nickel-phthalocyanine trisulphochloride obtainable by the action of chlorosulphonic acid on copperor nickel-phthalocyanine, in the form of the moist suction filter cake thoroughly washed with ice-water, the procedure being otherwise the same as that of Example 49; reactive dyestuffs yielding clear blue shades are then likewise obtained.

By following the procedure of Example 49, but starting from 87 parts of copper-phthalocyanine trisulphochloride and using, instead of 50 parts of the sodium salt of 1,3-diaminobenzene-4-sulphonic acid, 90 parts of the sodium salt of 4,4-diamino-diphenyl- 2,2'-disulphonic acid or 90 parts of the sodium salt of 4,4-diaminostilbene-2,2-disulphonic acid, reactive dyestufis are again obtained which dye cellulose materials by one of the methods mentioned above, in clear blue shades fast to wet processing, rubbing, and light.

When starting from 4,4",4",4"-tetraphenyl-Cuphthalocyanine, there is obtained after sulphochlorination, reaction with l,3-phenylene-diamine-4-sulphonic acid and acylation with 3,5-dichloro-isothiazole-4-carboxylic acid chloride, a reactive dyestuff which dyes cellulose materials in the presence of acid-binding agents in clear green shades fast to wet processing and light.

EXAMPLE 50 In 700 parts of water are dissolved 71 parts of the amino-anthraquinone dyestuff obtained by the reaction of l-amin0-4-bromo-anthraquinone-Z-sulphonic acid with excess 4,4'-diamino-diphenyl-2,2'-disulphonic acid and 27 parts of 3,5-dichloro-isothiazole-4-carboxylic acid chloride are added at 30C with good stirring, and a pH of 6-7 is maintained by the continuous addition of a sodium carbonate solution. When amino groups can no longer be detected. the resultant dyeslull of the formula O NH:

ll $5 OaNtl S OQNB salted out, filtered off with suction, washed and dried at 40C in a vacuum. It dyes cotton and regenerated cellulose by one of the methods mentioned above, in blue shades fast to wet processing, rubbing, and light.

By proceeding as described in Example 50, but using, instead of 71 parts of the starting dyestuff there employed, equivalent amounts of one of the following derivatives of l-amino-4-(aminoarylamino)- anthraquinone-2-sulphonic acid, similar dyestuffs are obtained in the dyeings which are likewise blue and have fastness properties similar to those of the dyestuff obtained above: l-amino-4-(4-amino-2-sulphophenylamino)-anthraquinone-2-sulphonic acid, l-amino-4- (4'-aminophenylamino)-anthraquinone-2,6- disulphonic acid, isomeric mixture of l-amino-4-(4- aminophenylamino)-anthraquinone-2,5- and -2,8- disulphonic acid, isomeric mixture of l-amino-4-(4- amino-2'-sulphophenylamino)-anthraquinone-2,5- and -2,8-disulphonic acid, isomeric mixture of l-amino-4- (3-amino-phenylamino)-anthraquinone-2,5- and -2,8- disulphonic acid, l-amino-4-(3-aminophenylamino)- anthraquinone-2,-disulphonic acid, l-amino-4( 3 amino-4-sulphophenylamino)-anthraquinone-2- sulphonic acid. With l-amino-4-(4-[4"-amino-2- sulpho-phenyl]-a.minophenyl)-anthraquinone-2,6- disulphonic acid, reactive dyestuffs are obtained which dye in bluish-grey shades.

EXAMPLE 51 By proceeding as described in Example 35, but using as starting material, instead of the copper-containing aminomonoazo dyestuff there employed, the equivalent amount of the chromium complex of the aminoazo dyestuff obtained by coupling diazotized lamino-2-hydroxy-3-chlorobenzene-5-sulphonic acid with l-[ 3 3 -aminophenyl l-sulphonylimidosulphonyl-phenyl-3-methyl-pyrazolone-(5), a reactive dyestuff is obtained which dyes cellulose materials by one of the methods described above, in yellow-brown shades of good fastness to wet processing, rubbing, and light.

EXAMPLE 5 2 In 3,000 parts by volume of water is dissolved at a pH H038 SO Na This solution is combined at a temperature of about 30C, while stirring, with a solution of 21.6 parts (0.1 mol) of 3,5-dichloro-1,2-isothiazole-4-carboxylic acid chloride in acetone. The mixture is stirred until the condensation is completed, the dyestuff is separated by the addition of a little sodium chloride and isolated. The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained which dissolves in water with a green color and dyes cotton by the methods described in Examples 1-3, in green shades.

A cotton fabric is impregnated with a solution at 2025C, which contains, per liter of liquor, 25 g of the above dyestuff and 0.5 g of non-ionic wetting agent (e.g. a polyethoxylated oleyl alcohol), 150 g of urea and 20 g of sodium carbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100 percent. After an intermediate drying at 5060C, the material is heated at 140C for 10 minutes and the dyeing thus obtained is thoroughly rinsed with hot water and treated at the boil for 20 minutes with a solution containing, per liter, g of Marseilles soap and 2 g of sodium carbonate. After rinsing and drying, a green dyeing of good fastness to wet processing, rubbing, and light is obtained.

Clear red shades of good fastness properties are also obtained on cellulose materials by one of the other dyeing or printing processes described in Examples 1-3, 12, and 22.

EXAMPLE 5 3 In 2,000 parts by volume of water is dissolved at a pH of 6, 0.1 mol of a paste of the aminoazo compound of the formula l HOaS O CuO 80311 which is obtained by coupling the diazonium compound from 6-acetamino-2-aminonaphthalene-4,8- disulphonic acid with 2-hydroxynaphthalene-3,6- disulphonic acid, and saponification and conversion of the monoazo compound into the copper complex. The resulting solution is combined with a solution of 21.6 parts of 3,5 dichloro-1,2-isothiazole-4-carboxylic acid chloride. The reaction mixture is stirred at 3035C, until the condensation is completed, the pH of the reaction solution being maintained at 6-7 by the addition of sodium carbonate. When the reaction is completed, the dyestuff is salted out, isolated and dried in a vacuum.

The dried dyestuff is a dark powder which dissolves in water with a violet color and dyes cotton in the presence of alkali, in bluish-violet shades.

EXAMPLE 54 An aqueous solution of 0.1 mol of the copper complex of the formula H03? 0 u o f N IhN- M WW7 N 80311 s oni prepared according to the instructions of German Patent Specification No. 1,061,460 or 1,085,988, is combined in the usual manner with a solution of 21.6 parts of 3,5-dichloro-l,2-isothiazole-4-carboxylic acid chloride in acetone. A pH of 6-7 is maintained by the addition of Na CO and when the reaction is completed, the dyestufi is isolated by salting out. In the dry state, it is a dark powder which dissolves in water with a violet color. Cotton fabrics are dyed in violet shades fast to light and wet processing.

EXAMPLE 5 5 In 150 parts of water are dissolved 27.5 parts of 2- methylamino-S-hydroxynaphthalene-7-sulphonic acid sodium salt, mixed with 21.6 parts of 3,5-dichl0ro-1,2- isothiazole-4-carboxylic acid chloride and stirred at 3540C for 30 minutes, while continuously neutralizing the resultant hydrochloric acid to a pH of 4-6 with a total of 34 parts by volume of a 16 percent sodium carbonate solution. The acylation is completed after about 2 hours, the pH is 6 and changes no more.

Thirty parts of sodium bicarbonate are then added, and a diazo suspension from 34 parts of the disodium salt of 2-aminonaphthalene-1,7-disulphonic acid in 200 parts of water is added dropwise at 40C within 15 minutes. The orange colored reactive dyestuff immediately formed, of the formula is further stirred for 1 hour, then completely separated by the addition of parts of sodium chloride, filtered off, washed with a dilute sodium chloride solution and dried at 45 in a vacuum. The dyestuff dyes cellulose materials by the methods mentioned above, in reddishorange shades of very good fastness to wet processing, and good fastness to chlorine.

By using in this example, instead of 21.6 parts of 3,5- dichloro-l,2-isothiazole-4-carboxylic acid, equivalent amounts of 3,5-dibromo-l,2-isothiazole-4-carboxylic acid bromide, a reactive dyestuff is obtained ieich dyes in orange shades and the dyeing properties are similar to those of the corresponding 3,5-dichloro derivative.

Orange to red reactive dyestuffs are obtained in an analogous manner by acylation of the aminonaphtholsulphonic acids listed in Column 3 of the following table with 3,5-dichloro-l,2-isothiazole-4-carboxylic acid chloride and coupling the resultant acylaminonaphthol-sulphonic acids with the diazo components mentioned in Column 2.

amino)-S-hydroxynaphtha- 2-aminonaphthalenel,5-disulphonic acid 2-aminonaphthalene- 1,5 ,7-trisulphonic acid 2aminonaphthalene- 1,5 ,7-trisulphonic acid 2-aminobenzenesulphonic acid Z-aminonaphthalenel-sulphonic acid II it 2-aminonaphthalenel,5-disulphonic acid Z-aminonaphthalene- 1,7-disulphonic acid Z-aminonaphthalenel,7-disulphonic acid 2-aminonaphthalenel ,5,7-trisulphonic acid l -amino-4-chlorobenzene-Z-sulphonic acid l-amino-2-methoxybenzeneJ-sulphonic lene-7-sulphonic acid 2-amino-S-hydroxynaphthalene-7-sulphonic acid 2-amino-5-hydroxynaphthalene-1,7- disulphonic acid 2-amino-8-hydroxynaphthalene-6-sul- 65 phonic acid 2-amino 8-hydroxynaphthalene-3,6- disulphonic acid 2-methylamino-5-hydroxynaphthalene-7-sulphonic acid 2'ethylamino-5-hydroxynaphthalene-7-sulphonic acid 2-(p-hydroxyethylamino)- S-hydroxy-naphthalene- 7-sulphonic acid 2-amino-5-hydroxynaphthalene-7-sulphonic acid 2-amino-5-hydroxynaphthalene-1,7- disulphonic acid 2-amino-8-hydroxynaphthalene-G-sulphonic acid 2-amino8-hydroxynaphthalene-3,6- disulphonic acid Z-amino-S-hydroxynaphthalene-1 sulphonic acid Z-methylamino-S-hydroxynaphthaleneJ-sulphonic acid 2-amino-8-hydroxynaphthalene-6-sulphonic acid Z-methyIammo-S-hydroxynaphthalene-7-sulphonic acid 2-(fl-hydroxyethylamino)- S-hydroxy-naphthalene- 7-sulph0nic acid 2-amino-8 -hyd roxynaphthalene-6sulphonic acid l-amino-B-hydroxynaphthalene-6-sulphonic acid l-amino-8-hydroxy naphthalene-3,6- disulphonic acid l-amino-S-hydroxynaphthalene3,6-

orange orange scarlet scarlet orange orange orange orange orange scarlet scarlet orange orange scarlet orange orange scarlet scarlet orange bluishred bluishred bluishred bluishred bluish red bluishred bluishred bluishred bluishred bluishred bluishred acid disulphonic acid 88 l-amino-benzene-2- l-amino 8-hydroxybluishcarboxylic acid-4- naphthalene-3,6 red sulphonic acid disulphonic acid 89 l-amino-4-acetyll-amino-8-hydroxyviolet aminobenzene-2- naphthalene-3,6- sulphonic acid disulphonic acid 90 l-amino-8-hydroxybluishnaphthalene-4,6- red disulphonic acid EXAMPLE 91 is salted out, filtered off, again dissolved in 4,000 parts of water at 60C, filtered and separated from the filtrate in a completely pure state by the addition of 400 parts of sodium chloride. The dyestuff is dried in the usual manner at 45C in a vacuum. It dyes cellulose materials by one of the methods mentioned above, in fast yellowish-orange shades.

EXAMPLE 62 3 ,5-dichloro-1 ,2-isothiazole-4-carboxylic acid chloride, 21.6 parts, is added to a neutral solution in 500 parts of water of 60 parts of the trisodium salt of the aminoazo dyestuff obtained by coupling diazotized 2-amino-naphthalene-3,6,8-trisulphonic acid with 3- acetylamino-aniline in an acetic acid medium, and the mixture is stirred at 45C for 6 hours, a pH of about 6 being maintained by the continuous addition of a sodium hydroxide solution. The partially precipitated acylation product is completely separated at a pH of 6.5 by the addition of parts of sodium chloride, and filtered off. For purification, the dyestuff thus obtained can be redissolved in 2,500 parts of water at 60C, clarified and separated again by salting out the warm filtrate with 350 parts of sodium chloride. The dyestuff has the formula SO Na SOJNB NH'COCIL; 01/ \S/ and after filtering off, drying at 45C and grinding, it is a yellow powder which readily dissolves in water, with a yellow color and dyes cellulose fibers by one of the dyeing methods mentioned above, in the presence of acidbinding agents, in very fast reddish-yellow shades. Fast yellow shades are also obtained on wool and polyamide fibers.

Similar dyestuffs are obtained by proceeding as described above, but using, instead of 60 parts of 4'- amino-2-acetyI-amino-phenyl-( I )-azo-naphthalene- (2)-3,6,8-trisulphonic acid sodium salt, corresponding quantities of the aminoazo dyestuff obtained from the amino compounds given in Column 2 and the coupling components given in Column 3 in the usual manner by diazotizing and coupling in an acetic acid medium, and acylating with 3,5-dichlorol ,2-isothiazole-4-carboxyl- IC acid chloride.

Ex. Diazo Coupling Shade on No. component component cotton 93 2-aminonaphthalene- I-amino-S-methylstrongly I ,S-disulphonic -methoxybenzene reddishacid yellow 94 I-amino-3- yellow methylbenzene 95 I-aminonaphthalenereddishfi-sulphonic acid yellow 96 I-amino-3-acetylyellow amino-benzene 97 3-aminophenyl urea yellow 98 l-amino-3-hydroxyyellow acetylaminobenzene 99 2-aminonaphthalenb-amino-El-methylstrongly 5,7-disulphonic acid 6-methoxybenzene reddishyellow IOO I-aminonaphthalenereddish- 7-sulph0nic acid yellow IOI I-amino-3-acetylreddishaminobenzene yellow I02 3-aminophenyl urea reddishyellow IO3 I-amino-3-hydroxyreddish acetylaminobenzene yellow I04 l-aminonaphthalene- I-amino-3-methylstrongly 3,7-disulphonic acid o-methoxy benzene reddishyellow I05 I-amino-3-methylreddishbenzene yellow I06 I-aminonaphthalenereddish- 6-sulphonic acid yellow I07 Z-aminonaphthalenel-amino-3 methyl reddish- 3,6-disulphonic acid benzene yellow I08 I-amino-3-methylstrongly 6-methoxybenzene reddish yellow I09 l-amino-3-acetylreddish aminobenzene yellow IIO 3aminophenyl urea reddishyellow lII Z-aminonaphthalene- I-amino-3-hydroxyreddish- 3,6-disulphonic acid acetylaminobenzene yellow II2 2-aminonaphthalene- I-aminonaphthalenereddish- 3,6-disulphonic acid -sulphonic acid yellow I13 2-aminonaphthalenel-amino-3-acetylreddish- 6,8-disulphonic acid aminobenzene yellow I14 2-aminonaphthalenel-amino2-methoxystrongly 6,8-disulphonic acid naphthalene-oreddishsulphonic acid yellow IIS 2-aminonaphthalenel-aminonaphthalene-G- reddish- 6,8-disulphonic acid sulphonic acid yellow ll6 Z-aminonaphthalene- I-aminonaphthaleneyellow 4,8-disulphonic acid 6-sulphonic acid I17 2-aminonaphthalene- I-aminonaphthaleneyellow 4,8-disulphonic acid 7-sulphonic acid Il8 2-aminonaphthalene- I-amino-2-methoxystrongly 4,8-disulphonic acid naphthalene-6 reddishsulphonic acid yellow II9 I-methylamino-3- yellow methylbenzene I20 l-ethyIamino-3- yellow methylbenzene I2I N-methylaniline yellow I22 N-ethylaniline yellow I23 N-(fi-hydroxyethyhyellow aniline I24 N-butylaniline yellow I25 2-aminonaphthaleneaniline reddish 3,6,8-trisulphonic yellow acid I26 I-amino-3-methylbenzene reddish yellow I27 3-aminophenyl urea reddish yellow I28 I-amino-3-hydroxy reddishacetylaminobenzene yellow I29 I-amino-3-acetylyellowish I30 2-aminonaphthalene- 3 ,6,8-trisulphonic amino-6-methoxybenzene I -amino-3-acetylamino-6-methylacid benzene I3I I-amino-3-methanesulphonyI-aminobenzene I32 2,5-dimethoxyaniline I33 3-methyl-6-mcthoxyaniline I34 N-methylaniline I35 Nethylaniline I36 N-butylaniline I37 N-(fi-hydroxyethynaniline I38 3-(N-ethylamino)-toluene I39 2-aminotoluene I40 I-amino-2.5-dimethylbenzene I41 l-amino-2- methoxybenzene I42 I-amino-3- methoxybenzene I43 Iethylamino-3- methoxybenzene I44 I-aminonaphthalene- 6-sulphonic acid I45 I-aminonaphthalene- 7-sulph0nic acid I46 2'aminonaphthalenel-amino-3-methyl- 4,6,8-trisulphonic benzene acid I47 I-amino-3-acetylaminobenzene I48 l-aminonaphthalenel-amino-3-methyl- 2,4,7-trisulphonic benzene acid I49 I-aminonaphthalene- I-aminonaphthalene- 2,4,7-trisulphonic 6-sulphonic acid 4-nitro-4'-aminol-amino-3-acetylstiIbene-2,2'- aminobenzene disulphonic acid I51 3-aminophenyl urea I52 I-amino-3-hydroxyacetylaminobenzene I53 N-methylaniline I54 N-ethylaniline I 55 N-butylaniline I56 N-(B-hydroxyethyhaniline I57 I-(N-ethylamino)-3- methylbenzene I58 aniline-2,5- I -aminonaphthalenedisulphonic acid 6-sulphonic acid I59 I-aminonaphthalene- 7-sulphonic acid I-amino-3-methylbenzene I 6 l g l-amino-B-acetylaminobenzene I62 I-amino-2-methoxy- S-methylbenzene I63 I-amino-2,5-dimethoxy I64 aniline-2,4-

disulphonic acid -orange reddishyellow reddishyellow yellowishorange yellowishorange reddishyellow reddish yellow reddishyellow reddishyellow reddishyellow reddishyellow strongly reddishyellow strongly reddishyellow reddishyellow reddishyellow reddishyellow reddishyellow reddish yellow reddishyellow yellow yellow reddishyellow reddishyellow reddishyellow reddishyellow reddish yellow reddishyellow reddishyellow reddishyellow reddishyellow reddishyellow yellow yellow reddishyellow reddishyellow reddishyellow EXAMPLE In 700 parts of water are dissolved neutral 65 parts of is salted out, filtered off, washed and dried at 40-50C. The dyestuff dyes cellulose materials in very fast ruby shades by one of the methods described above.

Dyestuffs of similar properties are obtained in a manner analogous to the method described above from the copper complexes of the azo dyestuffs prepared from the diazo and azo components listed in the following table.

Ex. shade on cotton Diazo component Coupling component 166 l-hydroxy-Z-aminobenzene-4-sulphonic acid Z-methylamino-S- hydroxy-naphthalene- 7-sulphonic acid 2-ethyl-amino-5- hydroxy-naphthalene- 7-sulphonic acid 2-(B-hydroxyethylamino)- S-hydroxy-naphthalene- 7-sulphonic acid 2-amino-8-hydroxynaphthalene-3,6- disulphonic acid ruby ruby

ruby

169 ruby 170 l-hydroxy-2aminobenzene-4,6-disulphonic acid l-hyd roxy-2-aminobenzene-S-sulphonic acid I79 l-hydroxy-Z-amino- Z-amino-S-hydroxy naphthalene l ,7- disulphonic acid 2-amino-8-hydroxynaphthalene-3,6- disulphonic acid 2-methylamino-5- hydroxy-naphthalene- 7-sulphonic acid 2-ethylamino-5- hydroxy-naphthalene- 7-sulphonic acid Z-(B-hydroxyethylamino)-5-hydroxynaphthalene-7- sulphonic acid l-amino-B-hydroxynaphthalene-3,6 disulphonic acid l-amino-8-hydroxynaphthalene-4,6- disulphonic acid l-amino-S-hydroxynaphthalene 3,6- disulphonic acid l-amino-8-hydroxy naphthalene-4,6-disulphonic acid l-amino-8 -hydroxy- 4-acetylaminobenzene naphthalene-3,6-

6-sulphonic acid I80 l-hydroxy-Z-aminodisulphonic acid l-ethoxy-8-hydroxy- 4-acetylaminobenzenenaphthalene-3,6-

6-sulphonic acid disulphonic acid ruby ruby

ruby

ruby

ruby

violet violet violet violet bluishviolet bluishviolet saponified 181 l-amino-S-hydroxyblue naphthalene2,4- disulphonic acid 182 l-amino-S-hydroxyblue naphthalene-2,4,6- trisulphonic acid 183 l-hydroxy-Z-aminol-amino-S-hydroxyblue G-acetylaminonaphthalene-2,4- benzene-4-sulphonic disulphonic acid acid (ti-positioned acetylamino group saponified) 184 l-amino-Z-hydroxyl-amino-S-hydroxyblue -nitronaphthalenenaphthalene-2,4- 4-sulphonic acid disulphonic acid (fi-positioned nitro group subsequently reduced to 185 l-amino-Z-hydroxyl-amino-8-hydroxyblue 6-nitronaphthulene naphthalene-2,4,6- 4-sulphonic acid trisulphonic acid (6-positioned nitro group subsequently reduced to 1) I86 l-hydroxy-Z-uminoblue 6-acetylaminobenzenc- 4-sulphonic acid (6-positioned acetylamino group saponified) EXAMPLE 187 Following the procedure of Example 22, except that the diazotized intermediate product containing reactive groups is coupled in a sode-alkaline medium with 40 parts of the sodium salt of l-acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid, in place of 47 parts of the sodium salt of 1-benzoylamino-8-hydroxynaphthalene3,6-disulphonic acid, and the resultant dyestuff of the formula is isolated in the manner described in Example 22. The water-soluble dyestuff dyes cellulose materials by the pad-steaming or pad-thermofixing method (at 140C) in white-dischargeable bluish-red shades which are fast to wet processing, rubbing, and light.

EXAMPLE 1 8 8 A solution of 19.5 parts of the sodium salt of lamino-benzene-4-sulphonic acid and 6.9 parts of sodium nitrite in 200 parts of water is allowed to run into a mixture of parts of ice and 28 parts by volume of concentrated hydrochloric acid; the mixture is then stirred at 0l 0C for 30 minutes and the excess nitrous acid is subsequently removed. To the diazo suspension thus obtained there is added at OlOC the cooled and thus partially recrystallized solution of 26.2 parts of the potassium salt of l-aminonaphthalene-8-sulphonic acid in 250 parts of hot water and the strongly acidic coupling mixture is neutralized at l0-20C to a pH of 4 by carefully adding a sodium hydroxide solution. The coupling is rapidly completed; the aminoazo dyestuff formed is completely salted out with 100 parts of sodium chloride, filtered off with suction, washed and redissolved in 400 parts of water at 50C at a pH of 6-7. The aqueous solution is mixed with 21.6 parts of finely powdered 3 ,S-dichlorol ,2-isothiazole-4-carboxylic acid chloride and stirred at 4550C for 1 hour, while continuously neutralizing the liberated hydrochloric acid to a pH of 5 with a sodium carbonate solution. When no more aminoazo dyestuff is indicated, the partially precipitated reactive dyestuff of the formula is salted out with 40 parts of sodium chloride, filtered off and redissolved in 800 parts of warm water for purification. After clarifying the solution, the pure dyestuff is separated from the filtrate by the addition of 80-100 parts of sodium chloride. After filtering off, drying at 45C and grinding, a yellow powder is obtained which readily dissolves in water, with a yellow color, and dyes cellulose fibers by one of the dyeing methods mentioned above in the presence of acid-binding agents in yellow shades of very good fastness to wet processing, light and chlorine. Fast yellow shades are also obtained on wool and polyamide fibers.

By proceeding as described above, but coupling, instead of 19.5 parts of the sodium salt of laminobenzene-4-sulphonic acid, equivalent amounts of the diazo components listed in the following table with l-aminonaphthalene-8-sulphonic acid, followed by acylation with 3,5-dichloro-1,2-isothiazole-4-carboxylic acid chloride, valuable yellow to brown reactive dyestuffs are also obtained.

Shade on cellu- Diazo component lose fibers 1-aminobenZene-2,5-di$ulph0llic acid Reddish-ycllow. 2-amino-naphthalene-4,8-disulphonie acid Strongly rcddish-yellow. Z-amino-naphthalene-5,7-disulphonic acid Do. 2-amino-naphthalenc-6,8-disulphonic acid. Do. 2-amino-naphthalene-3,6,8-trisulphonic aci D0. Z-amino-naphthalone-4,6,8-trisulphonic acid Do. 4-amin0-az0benzcne-3,4-disulph0nlc acid Yellowishbrown. 4-ami1n0-2-acetylamino-azobenzene-Z,5-disulphonic Orange-brown.

aci

S O;Na Reddishbrown.

l S OaNa (l-aminobenzene-2,5-disulphonic acid coupled with l-amino-naphthalene-G-sulphonic acid in an acidic medium).

(l-amino-naphthalene-2,5,7-trisnlphnic acid coupled with 1-amino-naphthalcne-G-sulphonic acid in an acidic medium).

'l':\hlc-('ontinucd Shade on ccllu- Dmzo component losc flhcrs S O Na 0 (1 ll ltcrldlsh- 5 brown.

| N30; S C II;

S OaNa (l-amino-naphthalone-2,5,7-trisulphollic ncld coupled with l-amino-Lmctlioxy-S-rncthyllmizcno in an acidic medium).

EXAMPLE 189 When a cellulose fabric is printed with a printing paste which contains, per kilogram, g of the dyestuff described in Example 12, 100 g of urea, 300 g of water, 500 g of alginate thickening (60 g of sodium alginate per kilogram of thickening), 10 g of sodium carbonate and 10 g of the sodium salt of 3-nitrobenzene-sulphonic acid and which was made up with water to 1 kg, subsequently subjected to intermediate drying and then steamed in a suitable steaming apparatus at 103-l 15 C for 30 seconds, rinsed and boiled with soap, an intense bluish-red print of good fastness to wet processing, rubbing, and light is obtained.

EXAMPLE 190 A mixture of the solutions of 65.5 parts each of the 2:1 chromium complex and the 2:1 cobalt complex of the dyestuff of the formula SO Na each time, in 400 parts of water, is stirred with parts of finely powdered 3,5-dichloro-l,2-isothiazole-4-carboxylic acid chloride at 45C for about 10 hours, while maintaining a pH of 4.5-5.5. When no more aminoazo dyestuff can be detected by chromatography (Co-complex: blue; Cr-complex: blue-green), the resultant mixture of the two reactive dyestuffs is salted out with potassium chloride, filtered off and dried.

The dyestufi yields on cellulose materials by the padding processes or by printing in the presence of acid-binding agents intense black shades of very good fastness to wet processing and light.

By proceeding in an analogous manner, but using a mixture of the 2:1 chromium-complex and the 2: lcobalt-complex of the following aminoazo dyestuffs, valuable black dyestuffs are likewise obtained.

Diazo Coupling Coupling component component pH l-hydroxy-Z-amino-4- l-hydroxy-8 -amino 9 nitrobenzene naphthalene-3 ,6- disulphonic acid l -hydroxy-2-amino-4- 9 nitronaphthalene-7- sulphonic acid EXAMPLE 191. W o 3 ,S-Dichloro-l ,2-isothiazole-4-carboxylic acid chloride, 21.6 parts, is added to a neutral solution in 300 parts of water, of 53.15 parts of the disodium salt is filtered off, dissolved warm at a pH of 6-7 in 3,000 parts of water and reprecipitated from the filtered solution by the addition of sodium chloride. After filtering off, drying and powdering, a yellow powder is obtained,

f the amlIlOaZO dyestuff Obtained y plmg which IS readily soluble in water and dyes cellulose diazotized l-am1no-4-nitro-benzene-2-sulphon1c acid mammals from along bath at 40C or by the cold-pad- I I Wllh P P yD- y batch process with the use of sodium carbonate as acidpy 'w) and subsequent reductlon 0f the IlltfO binding agent, in clear yellow shades fast to washing, group with sodium sulphide, and the mixture is stirred bbi d1i h at 45-50C for two hours, while continuously neutrahz- B mceedin as described above but Sin instead mg the liberated hydrochloric acid to a pH of 4-6 with y p g of the ammoazo dyestuff there employed, equivalent a sodium carbonate solution. The separated dyestuff of amounts of the armnoazo dyestuffs synthesized from the formula SO Na the components listed in the following table, valuable 1 5 new reactive dyestuffs are likewise obtained. ClCC-C 0HN N=NCC CH 11 H In the table, the term saponified means that an N C 01 Ho acylamino group contained in the ammoazo dyestufi S was subsequently saponlfied, while the term reduced means that a nitro group contained in the draw com- 01 ponent is reduced, after coupling, to the amino group, N 8 whereby the des1red ammoazo dyestufi is formed.

pH of Example coupling Shade on No. Diazo component zo component medium cellulose 192 1-amino-4-nitrobenzene-Z-sulphonic acid 1-(4-sulphophenyl)-3-methylpyrazolone-(5) 5-6 Yell w.

-posi oned nitro group subsequently reduced) 193 1-amino-4-nitrobenzene-2-sulphonic acid 1-(4-sulph0phcny1)-3-carboxypyrazol0ne-(5) 5-6 Reddish-yellow. 194 do 1-(3-sulphephenyl)-3-methyl-5-amino-pyrazole 6 7 D0. 195 1-amino-3-acetylaminobenzene-fi-sulphonic acid do 6-7 Do.

(3 positioned acetylamino group subsequently saponified) 196 l-amino-3-acetylaminobenzene-fi-sulphonic acid l-(fl-hydroxyethyl)-3-methy1pyrazolene-(5) 5-6 Do. 197 2 mol 1-amino-3-acetylaminobenzeneo-sulphonic l-mol bis-pyrazolenc from 4, 4-bis-hydrazino- 5-6 Do.

acid (saponified). dibenzyl-2, 2-disulphonic acid and acetoacetic ethyl ester. 198 1 mol l-amino-s-acetylamjnobenzene-fisulphonic 1-(4-sulph0phcnyl)-3-carboxypyrazolene-(5) fi-6 Do.

acid (saponified). 199 1-amino-5-acety1aminonaphthalenc-3,7-disuld0 5-6 Do.

phonic acid (saponified). 200 c. l-amino-Z-methyl-benzcnc-i,6-disulphonic acid 2-a(cctyln.prurii(;-5-naphthol-7-sulphonic ucid 7-8 Orange.

sapon 1e 201 do 2-acctylamln0-8-naphth0l-6-sulphonic acid 7-8 Red.

(suponified). 202 do Lchloro-Z-acctylomino-b-nuphthnl-Wsulplionic acid 7-8 Orange.

(saponified). 203 l-aminobenzone-2-sulplionic acid l-acetylamlnO-B-hYdfOXYflfiPhtl10.101104,li-disul- 7-8 Red.

phonic acid (saponilicd). 204 2-aminonapl1thalcne-3,G-disulphcnic acid do 7-8 Bluish-red. 205 Z-aminonaphthalene-li, 7-disulph0nic acid do- 7-8 Do. 206 2-aminonaphthalcnc-4, B-disulphonic acid... d0 7-8 D0. 207 2-aminonaphthalcne3,fi-disulpllonic acid 1-acetylamino-B-hydroxynaphthniche-3, 6 7-8 Do.

disulphonic acid (saponificd). 208 2-aminonaphthalenc-4,8-disulphonic acid do 7-8 D0. 209 l-arnino-4-methoxybenzene-2-sulphonic acid 2-(N- cetyl-N-methylamino)-5-hydroxynaphtha- 7-8 Ycllowish-red.

lene-7-sulphonic acid (saponified). 210 do 2(N-aeetyl-N-methylamino)-8-hydroxynaphtl1alene 7-8 Red.

-6-sulphonic acid (saponified). l arninobenzene-2-sulphonic acid do c 7-8 Red. A" l-aminobeuzene-Bsulphonie acid 7-8 Rod. 1-aminobenzeneA-sulphonic acid 7-8 Red. 214 1-:imin0-4-mcthylbenzene-Z-sulphonieucid. 7-8 Red. 21d... l-umin0-2,4-dimetliylbenzcl\e-G-sulphouic acid 78 Red. 2111 "do cctyl 7-8 Red. I acid (saponified). 117 r V v a J10 2-ncetylamin0-8-hydr0xynapl1thalene-3,6-disul- 7-8 Red.

phonic acid (saponified). 218.. 4-nmmoazobcnzene-Zi,4-d1su1ph0me acid. l-umino 3-ucetylaminobcnzcnc 5-6 Yellow-brown. 2}! do 1-amino-3-hydroxyacetylaminobenzene. 5-6 D0. 22 do l-amino-naphthalene-fi-sulphonic acid 5-6 D0. 221 do l-amino-naphthalcnc-7-sulphonic aeid. 56 Do. 222 do l-amino'il-(4-amin0-2-sulph0phenyl-(l)-az0)-8- 8 Black.

hydroxynaphthalene-3,6-disi1lphonic acid.

methylaminophen yl )-am inoanthraquinone-2,5 '-disulphonic acid in l ,000 parts of water are dissolved 52.4 parts of the 228 "I'F "f a fl -a disodium salt of 4-( [4"-aminophenyl]-amino)-2'-nitro- 229 .,I,i, 3{'i, .m,. diphenyl-amino-3,4-disulphonic acid and stirred with t q lfifi'- su p n c a d 21.6 parts of 3,5-dichloro-l,2-isothiazole-4-carboxylic 'figggsgg 'zg acid chloride at 4550C for 5 hours. The liberated 231 l-amino-4-(3'-amlnophenyl)-amlnohydrochloric acid is continuously neutralized with sodi- 232 lIqflI:n0ne-2,54,4'itrisulphogiic alcid um carbonate to a pH of 4-6. The resultant reactive 'g fi 'f m'gazf T!g '2 mtro dyestufi' of the formula 10 trisulphonic acid Na03SNH-NHNH0Cfi-C-Ol I Cl-C N01 some is salted out, filtered ofi, washed and dried. The g g f f b I I h t d dyestuff dyes cellulose fibers from a long bath or by one fi i g; $933 38 p 6 of the customary padding processes in the presence of 233 l-amino-4-[4'(4"-aminobenzyl)-phenyl]- sodium carbonate as acid-binding agent in deep violet- 1 234 l-amino-4(4-methylaminophenyl)-am|nobrown shades fast to wet processing and rubbing. an,maquinongLsmphomc acid 235 lamino-4-(3'-methylaminophenyl)-amino- EXAMPLE 224 anthraquinoneZ-sulphonic acid I 236 l-amino-4-t2'-methylaminophenyl)-amino- A neutral solution of 54.7 parts of the dlSOdlUlTl salt amhraqumone-z-sul honic 301d I r -ammo- -am|no-nap t y- -am noof 1-am1no-4-(2 -methyl-3 -am1nophenyl)-am1no- 237 1 g z g i anthraquinone-2,5-disulphonic acid in 1,000 parts of 233 the condgnsafiorrpfoductofl molof water stirred with 21.6 parts of 3,5-dichloro-l,2- gy chlgflde isothiazole-4-carboxylic acid chloride at C for 4 30 2: i 1 hours. The liberated hydrochloric acid is continuously mo] of ethylene diamine (one-sided) neutralized to a pH value of 6.5-7 with a sodium car- "???fi t i xlx filgf fl mm bonate solution. When tflge rteiaction isl completed, the 12i rja ctive Ji m I c resultant reactive dyestu of e formu a o NHZ EXAMPLE 239 A some A solution of 107 g of a mixture of equal molar portions of copper-phthalocyanine-trisulphonic acid- S OaNa 40 (3 ,3 ,3 '-mono-( m-amino-p-sulphophenyl )-amide and L N copper-phthalocyanine-trisulphonic acid-3 ,3 ,3 )-di- H- (m-amino- -sul ho hen l)-amide is adusted to 1.3

P P P Y .1 m liters and a pH of 6; 32.5 g of 3,5-dichloro-l ,2-

li N isothiazole-4-carboxylic acid chloride are introduced at 20-25C. While stirring, the temperature is raised by EX. Watersoluble No. amino-anthraquinone derivative 225 l-amino-4-(3-arninophenyl)-aminoanthraquinone-2,5 -disulphonic acid 226 l-amino-4-(2'-chloro-3'-aminophenyl)- amino-anthraquinone-2,5'-disulphonic acid 227 l-amino-4-(2'-methyl-3' 5l0C per hour and finally kept at 45-50C for several hours. At the same time, a pH of about 6.1-6.9 is maintained by the dropwise addition of 3N NaOl-l, until on average each dyestuff molecule is provided with at least one dichloro-isothiazole-carboxylic acid amide radical; this can easily be ascertained by the consumption of sodium hydroxide solution, on the one hand, and by a determination of amino groups, on the other hand. The 3,5-dichloro-l ,2-isothiazole-4-carboxylic acid chloride can also be introduced in the form of a solution in acetone. For working up, the dyestuff solution may also be heated at the stated pH to C or more, without reducing the capability of the dyestuff to react with cellulose. Separation of unreacted 3,5- dichloro-l,2-isothiazole-4-carboxylic acid and of the saponification product formed therefrom is carried out by filtration or in a separator. The reaction product is precipitated by introducing g of sodium chloride per liter of dyestuff solution. The product is filtered off with suction and dried at about 50C in a vacuum or at normal pressure. 195-200 grams of crude dyestuff are 7 obtained, which still contains about 30 percent of sodium chloride. The common salt can be removed to a great extent by stirring the crude dyestuff with 250 ml of water and again filtering off with suction.

The dyestufi dyes cellulose materials by the padtherrnofixing process at 140C and by the pad-steaming process in turquoise shades fast to wet processing, rubbing, and light.

The dyestufi mixture used as starting material can be obtained by a method known as such, for example, by adding 3 mol of 2,4-diaminobenzene-sulphonic acid at -206.5 to an aqueous suspension of a copper-phthalocyanine-trisulphonic acid chloride which is free of sulphonic acid groups, and simultaneously catalyzing the saponification with 3 mol of pyridine, whereby the above-mentioned mixture of Pc-sulphonamides is formed.

A similar product is obtained by using as starting material a mixture which contains the stated components in a molar ratio of 4:1. This mixture is obtained from the same copper-phthalocyanine-trisulphonic toluylene-diarnine-2,4 )-sulphonic acid-( 5 4,4- diamino-dibenzyl-disulphonic acid-(2,2'), naphthylene-diamine-( 1,5 )-disulphonic acid-( 3 ,7).

Products of this type and their production have frequently been described in the patent literature. Their reaction with 3,5-dichloro-l,2-isothiazole-4-carboxylate acid chloride can always be carried out in the same way.

This applies also to the reaction of 3,5-dichloro-l,2- isothiazole-4-carboxylate acid chloride with the copperand nickel-phthalocyanine intermediates which lead to green reactive dyestuffs and are obtainable, for example, by polysulphochlorination of tetra- (3 ,3 ,3 ',3 )-(p-tolyl-mercapto)-copper-phthalocyanine with chlorosulphonic acid, condensation of l to 2 sulphochloride groups per molecule with 1,3-phenylene-diamine-4-sulphonic acid or 1,4-phenylenediamine-3-sulphonic acid, and saponification of the remaining sulphochloride groups; also the homogeneous or mixed amino groupand sulpho group-containing arylation and alkylation products of triand tetramercapto-copper- -nickel)-phthalocyanine can be converted into valuable green reactive dyestuffs in an analogous manner by acylation of their amino group with 3,5-dichloro-1,2-isothiazole-4-carboxylic acid.

EXAMPLE 240 By proceeding according to the instructions of Example 12, but coupling the dyestufli' intermediate obtained in the presence of 12 parts of sodium carbonate at a final pH of 7, with the diazo compound from 20.8 parts of 3-chloro-aniline-6-sulphonic acid, in place gf 28 A, the V diazo compound from 17.5 parts of 2- aminobenzene-sulphonic acid, a reactive dyestuff of the formula is obtained, with which cellulose materials can be dyed or printed by one of the padding or printing processes customary for reactive dyestuffs with the use of sodium carbonate as acid-binding agent, in brilliant red shades fast to wet processing.

In an analogous manner there are obtained from the coupling components listed in the following table by acylation of their amino group with 3,5-dichloro-l ,2- isothiozole-4-carboxylic acid chloride and coupling of the resultant dyestuff intermediates with the stated diazo components, valuable reactive dyestuffs with which cellulose materials can be dyed or printed,

preferably in the presence of sodium carbonate, in the shades as indicated.

Ex. Diazo Coupling Cou- No. component component pH shade 241 l-amino-4-methoxyl-amino-8-hydroxy 7-8 vio benzene-fi-sulphonic naphthalene-3,6-dilet acid sulphonic acid 242 l-amino-8-hydroxy- 7-8 redd naphthalene-4,6- ishdisulphonic acid violet 243 2-amino-5-hydroxy- 7 scar naphthalene-1,7- let disulphonic acid 244 1-amino-5-chloro- 7 ora bcnzene-2-sulphonic nge acid 245 l-aminobenzene-Il- 7 sulphonic acid 246 l-aminobenzene4- 7 sulphonic acid 247 2-amino-8-hydroxy- 7-8 scar naphthalene-3,6- let disulphonic acid 248 4-aminobenzoic acidl-amino-8-hydroxy- 7-8 red (B-sulpho-ethyhnaphthalene-3,6- amide disulphonic acid 249 l-amino4-sulpho- 7-8 vio acetylamino-benzenelet fi-sulphonic acid 250 l-amino-S-sulpho- Z-amino-S-hydroxy- 7 ora acetylamino-benzenenaphthalene-1 ,7- nge 6-sulphonic acid disulphonic acid 251 l-amino-4-sulpho- 7 scar acetylamino-benzene let 252 l-aminobenzene-2,4- l-(2'-methyl-3'- 6 yel disulphonic acid amino-5'-sulphophenyl)- low 3-methyl-pyrazolone-(5) 253 2-amino-naphthalene- 4,8-disulphonic acid EXAMPLE 254 By proceeding according to the instructions of Example 22, but coupling the dyestuff intermediate obtained from l,3-diaminobenzene-6-sulphonic acid and 3 ,5-dichloro-1 ,2-isothiazole-4-carboxylic acid chloride, after diazotization at 40C at a pH of 7.5-6.5,

with a solution of 40.5 parts of the disodium salt of 2- sulphoacetylamino-S-hydroxynaphthalene-7-sulphonic acid, a reactive dyestuff of the formula out i is obtained, which dyes cellulose materials by the usual methods of application with the use of sodium carbonate as acid-binding agent in fast orange shades.

EXAMPLE 25 When the procedure described in Example 191 is followed, but instead of the aminoazo dyestuff there employed, 53.15 parts of the disodium salt of the aminoazo dyestuff obtained by coupling diazotized 1- amino-4-nitrobenzene2-sulphonic acid with l-(2'- chloro-S -sulphophenyl )-3-methyl-pyrazole-( 5) and subsequent reduction of the nitro group with sodium sulphide, are acylated with 3,5-dichloro-l,2- isothiazole-4-carboxylic acid chloride, a valuable reactive dyestuff is likewise obtained, with which cellulose materials can be dyed or printed by the usual dyeing and printing processes in fast yellow shades.

Similar reactive dyestuffs are obtained by acylating instead of the aminoazo dyestuff mentioned above, an aminoazo dyestuff synthesized from the components listed in the following table with 3,5-dichloro-l,5-

sulphophenyI-Ilcarboxy-pyrozolone-( 5) EXAMPLE 264 In 700 parts of water are dissolved neutral 58 parts of the dyestuff having the formula prepared by coupling diazotized l-hydroxy-2-amino-4- chlorobenzene-S-sulphonic acid with 2-methylamino- 8-hydroxynaphthalene-6-sulphonic acid and coppering the resultant azo dyestuff, and 21.6 parts of finely powdered 3,5-dichloro-l,2-isothiazole-4-carboxylic acid chloride are added and the mixture is stirred at 4045 C, while continuously neutralizing the liberated hydrochloric acid to a pH of 5-6 with a sodium carbonate solution, until free amino groups can no longer be detected. The resultant reactive dyestuff of the formula isothiazole-4-carboxylic acid chloride: I Example Diazo A20 4 N:N No. component component Shade N 256 l-aminoA-nitrobenzenel-(2"methyl-4'- yellow 40 Naoas 2-sulphonic acid sulphophenyl)- 5 (reduced) 3-methyl-pyrazolone(5) C1 257 l-(2',5'disulphoyellow j" Y hen l)-3-mcth lgymziflongm y is salted out, filtered off, washed and dried at 40-50C. 258 l-( y yellow The dyestuff dyes cellulose materials by one of the 2': f methods described above, in very fast violet shades. pyrazolone(5) Dyestuff of similar properties are obtained in a 259 Ye"ow manner analogous to the method described above from 4 th 1 bt d b 1 d m l t 3 me,hy|pyram|one (5) e copper comp exes, o ame y simp e e-me a 26 l-amino-3-acelylaminvy s mg or oxidizing coppermg, of the monoand diazo benzene--sulphonic sulphop eny ye ow acid (saponifled) methylpyrazolone-(S) dyestufis produced from the diazo and azo components 261 l-(4'- ulphophenyl)- listed in the following table:

Example Coupling No. Diazo component Azo component pH Shade 265 1-hydroxy-2-amino-4-chlorobenzcnc-5-sulphonic acid. 2-amino 8-hydroxynaphthalene-3,G-disulphonic acid- 10 Reddish-violet. 266 do 1-amino8-hydroxynaphthalene3,6-disulphonicacid, 10 Bluish-violet. 267 2-am1no-naphthalene-4,6,8-trisulphomc acid Z-hydroxy-G-acetylaminonaphthaleneA-sulphonie 8-9 Reddish-blue.

(coppered with oxidation). (saponifiad). 268 l-amgnzqhhydgxy-fi-mtronaphthalene-4-sulphonic l-hydroxy-8-ethoxynaphthalene-3,6 disulphonic acid 10 Blue.

aci re uce 269 l-hydroxy-2-aminobenzene-4,G-disulphonic acid 2 hydroxy-3-aminonaphthalene-5,7-disulphonic acid. 10 Red. 270 Z-arnino-naphthalene-4,B-disulphonic acid d 8-9 Blue.

(coppered with oxidation). 27! Z-aminonaphthalene-t,6,8-trisulph0nic acid 2-hydroxy-3-aminonaphthalene-7-sulphonic acid 8-9 Do.

(coppercd with oxidation). 272 3-methoxy-4-amino-B-methylazobenzene-2,4- 2-methylamino-fi-hydroxynaphthelene-7-sulphonic 10 Navy blue.

disulphonic acid (coppered with demethylation). 273 do 2-amino-8-hydroxynaphthalenc-3,fi disulphonic acid 10 Do. 274 3-methoxy-4-amino-6-methylaz0benzene-2,4- 2-amino-5-hydroxynaphthalene-l,7-disulphonic acid. 10 Do.

disulphonic acid (compared with demethylation). 275 3-methoxy-4-amino-6-methylazobenzene-2,5- 2-methylamino-5-hydroxynaphthalcnc-7-sulphonic 10 Do.

disulphonic acid (coppercd with dcmethylation). acid 276 do 2-amino-B-hydroxynaphthalone-3,6-disulphonic acid. 10 D0. 277 d0 2-amino-5-hydroxynaphthalcnc-1,7-disulphonic acid 10 DO- EXAMPLE 278 By proceeding according to the instructions of Example 224, but using instead of the 54.7 parts of the disodium salt of l-amino-4-[(2'-methyl-3'-aminophenyl)-amino]-anthraquinone-2,S-disulphonic acid there mentioned, 63.5 parts of the trisodium salt of l-amino- 4-[ 3 '-aminophenyl )-amino]-anthraquinone-2,4 ,6 or -2,2',6- trisulphonic acid, a reactive dyestuff is obtained which dyes cellulose fibers by one of the usual dyeing methods in clear reddishblue shades of very good fastness to wet processing.

By using equivalent amounts of l-amino-4-(3- amino-phenyl-amino)-anthraquinone-2,5,8- trisulphonic acid, a valuable reactive dyestuff is likewise obtained which dyes cotton in fast greyish-blue shades.

EXAMPLE 279 In 300 parts of water are dissolved neutral 30.4 parts of 2-amino-8-hydroxynaphthalene3,6-disulphonic acid, heated to 45-50C, and 15.6 parts of 3,5- dichloro-l,2-isothiazole-4-carboxylic acid chloride are added. Thirty parts of a 15 percent sodium carbonate solution are added in the course of 5 hours so that the pH value is between 4 and 6. The acylation product partially precipitates.

A freshly prepared diazonium salt solution from 13.6 parts of p-aminobenzyl-sulphonic acid is added dropwise at 5C into a suspension of the acylation product, which has been mixed with 12.5 parts of sodium carbonate. After subsequent stirring for hours at ice-bath temperature, the product is salted out with sodium chloride, filtered off with suction, washed with a dilute sodium chloride solution and dried at 40C in a vacuum drier. The resultant dyestuff corresponds to the formula SO3N3.

By proceeding as stated above, but acylating instead of 304 parts of 2-amino-8-hydroxynaphthalene-3,6- disulphonic acid, 30.4 parts of 2-amino-5-hydroxynaphthalene-l,7-disulphonic acid with 3,5-dichlorol,2-isothiazole-4-carboxylic acid chloride and coupling the coupling component containing the reactive groups with diazotized p-aminobenzyl-sulphonic acid, a readily soluble reactive dyestuff is obtained which dyes fabrics containing cellulose fibers in brilliant reddishorange shades.

A cotton or cellulose fabric is impregnated on the foulard at 25C with a solution containing per liter of liquor, 30 g of the dyestuff described in paragraph 1 of the present example, 100 g of urea and 20 g of sodium carbonate, squeezed off to a moisture content of about 100 percent and the moist fabric is again rolled up. After standing at room temperature for 24 hours, the fabric is rinsed, boiled with soap in the usual manner, and dried. A brilliant scarlet dyeing of good fastness to wet processing and light is obtained.

A cotton or cellulose fabric is impregnated on the foulard at 20-25C with a solution containing per liter of liquor, 30 g of the dyestuff described in paragraph 1 of the present example, g of urea and 20 g of sodium carbonate, squeezed ofi to a moisture content of about 100 percent and steamed at 103C for 10 seconds. After rinsing, boiling with soap, and drying, a brilliant scarlet dyeing of good fastness to wet processing and light is likewise obtained.

A cotton fabric is impregnated with a solution at 2025C, which contains per liter of liquor, 20 g. of the dyestuff obtainable according to paragraph 1 of the present example and 0.5 g of a non-ionic wetting agent (for example, a polyethoxylated oleylalcohol) as well as 150 g of urea and 15 g of sodium bicarbonate. The fabric is subsequently squeezed off between two rubber rollers to a moisture content of about 100 percent. After an intermediate drying at 50-60C, the fabric is heated at C for 10 minutes and the dyeing thus obtained is thoroughly rinsed with hot water and treated at the boil for 10 minutes with a solution containing per liter, 5 g of Marseilles soap and 2 g of sodium carbonate. After rinsing and drying, an intense scarlet dyeing of good fastness to wet processing and light is obtained.

When a cellulose fabric is printed with a printing paste which contains, per kilogram, 30 g of the dyestuff described in paragraph 1 of the present example, 100 g of urea, 300 g of water, 500 g of alginate thickening (60 g of sodium alginate per kilogram of thickening), 10 g of sodium carbonate and 10 g of the sodium salt of 3- nitrobenzene-sulphonic acid and which is made up with water to 1 kg, the material is subsequently subjected to an intermediate drying and then steamed in a suitable steaming apparatus at 1031l5C for 30 seconds, followed by rinsing and boiling with soap, an intense scarlet dyeing of good fastness properties is obtained.

One hundred parts of wool are introduced at 40C into a bath which contains, in 5,000 parts of water, 1.5 parts of the dyestuff described in paragraph 1 of the present example as well as six parts of 30 percent acetic acid and 0.5 part of a polyethoxylated stearylamine derivative containing hydroxyl groups. The dyebath is brought to the boil within 30 minutes, and dyeing is then carried out at boiling temperature for 1 hour. After rinsing and drying, a brilliant scarlet dyeing of good fastness to washing, milling, and light is obtained.

EXAMPLE 280 2-aminol -methylbenzene-3 ,S-disulphonic acid (monosodium salt), 28.9 parts, is diazotized and the diazo compound is coupled with 13.7 g of l-amino-2- methoxy-S-methylbenzene in a weakly acidic medium. The resultant monoazo dyestuff is isolated and subsequently diazotized, or also immediately diazotized in solution without isolation, and coupled in an alkaline medium with 25.3 parts of 2-methyl-amino-5-hydroxynaphthalene-7-sulphonic acid. The diazo dyestuff obtained is salted out by the addition of sodium chloride, filtered off with suction, and the isolated product is metallized with about 50 parts of crystalline copper sulphate, 40 parts of diethanolamine and 50 parts of ammonia (d 0.88) at 95l00C within about 5 hours. The dyestuff is isolated from the coppering solution by the addition of salt and careful acidification.

The coppered amino-diazo dyestuff is then acylated in an aqueous solution at a pH of 46 and at a temperature of 45C with 21.5 parts of 3,5-dichloro-1,2-

isothiazole-4-carboxylic acid chloride, while maintaining the pH value within the stated range by the addition of sodium carbonate. When the acylation is completed, the dyestuff is isolated with sodium chloride and dried at 50C. In the form of the free sulphonic acid, the 5 dyestuff corresponds to the formula I 80311 CH3 HOsS It dyes cellulose fabrics by the processes known for reactive dyestuffs in navy blue shades fast to wet processing and light.

Further dyestuffs according to the invention can be produced in a similar manner, when the above-mentioned monoazo dyestuff from 2-amino-l-methylbenzene-3,5-disulphonic acid and 1-amino-2-methoxy- S-methylbenzene is combined with the aminonaphthol-sulphonic acids given below and with 3,5-

dichloro-l ,2-isothiazole-4-carboxylic acid chloride in accordance with the instructions given above.

Coupling component 2-amino-5-hydroxynaphthalene-1,7-disulphonic acid 2-amino-8-hydroxynaphthalene-3,6-disulphonic acid The resultant dyestuffs have a blue color.

EXAMPLE 281 tion at C and a pH value of 4-6, and acylated after 45 30 minutes at a pH value of 4-6 and at a temperature of 45-60C with 0.1 mol of 3,5-dichloro-l,2-isothiazole- 4-carboxylic acid chloride. The resultant dyestuff of the formula N i-Cl is salted out. A blue dyeing is obtained on cotton.

EXAMPLE 282 A neutral paste of copper-phthalocyanine-3,3,3"- trisulphonic acid chloride prepared from 600 g of technical 96 percent copper-phthalocyanine is stirred with a little water, adjusted to 1 liter and reacted at a pH of 3.5-6.0 with 216 g of N-methyl-N-(4'-arnino-2'- sulphobenzyl)-amine, initially at 03C, finally at 2035C, with the addition of 300 ml (295 g) of pyridine, and the pyridine is then distilled off from the resultant solution of copper-phthalocyaninedisulphonic acid-monosulphonic acid-( 3 -sulpho-4 methyl-aminomethyl-anilide) at a pH of 9.0 with steam. Two hundred eighty grams of finely powdered 3,5- dichloro-l,2-isothiazole-4-carboxylic acid chloride are added in portions in the course of 4-6 hours to the solution which has been cooled to 30C, while maintaining a pH of 7.5-9.5 by the addition of a dilute sodium hydroxide solution. At the same time the reaction mixture is diluted with water as required, so that the dyestuff always remains dissolved.

A dyestuff solution of 10 liters is obtained which is separated from the excess acylating agent, adjusted to a pH of 7.0 by the addition of acetic acid and the dyestuff is precipitated by adding 2.5 liters of a concentrated sodium chloride solution while stirring.

After filtering off with suction and drying at 50C, a clear turquoise-blue dyestuff is obtained, which is fixed on cotton from a soda-alkaline solution at 90C with a very good yield and very good fastness to washmg.

By using the NiPc-3,3 ,3"-trisulphonic acid chloride as starting material, a turquoise-blue shade of equally valuable properties is obtained, which is only slightly more greenish.

EXAMPLE 283 In parts by volume of concentrated hydrochloric acid are dissolved 12.5 parts of 3-amino-4- sulphobenzyl-N-methylamine and 4-parts of sodium nitrite in 20 parts by volume of water are added dropwise to the solution. The resultant clear diazonium slat solution is added dropwise at 30-35C to an aqueous solution of the equimolar amount of l-N-benzoylamino-8-hydroxynaphthalene-4,6-disulphonic acid and 16 parts of sodium bicarbonate in 200 parts by volume of water.

The dyestuff partially precipitates and is redissolved by the addition of 2,000 parts by volume of water. Fifteen parts of 3,5-dichloro-l,2-isothiazole-4-carboxylic acid chloride are then added at 4050C. The pH is kept between 7 and 8 by the dropwise addition of a sodium carbonate solution. When the acylation is completed, as can be recognized from the consumption of sodium carbonate, the dyestuff is separated with 10% of sodium chloride, filtered off with suction, pressed off and dried in a vacuum drier at 40C. The bluish-red dyestuff obtained corresponds, in the form of the free acid, to the formula The dyestuff obtained from 6-nitro-2-diazo-1- hydroxy-benzene-4-sulphonic acid and 2-hydroxynaphthalene by soda-alkaline coupling, 38.9 parts, is stirred at a pH of 8 in 200 parts of water at a temperature of 7080C. 67.9 parts of the chromium complex compound of the azo dyestuff from 4-chloro-2-diazo-1- hydroxybenzene--su[phonic acid and l-amino-8- hydroxy-naphthalene-3,6-disulphonic acid containing l-chromium atom per dyestuff molecule are introduced into this suspension, while maintaining a pH between 7 and 9 by the dropwise addition of a sodium carbonate solution. After 20 minutes at 7080C, a dark blue solution has formed. The paper chromatogram shows that a homogeneous mixed complex has formed. The mixed complex is acylated with 30 minutes at 45C and a pH of 4-6 with 21.6 parts of 3,5- dichloro-1,2-isothiazole-4-carboxylic acid chloride, the pH being kept within the stated range by the dropwise addition of a sodium carbonate solution. The acylated dyestufi is salted out with 20 percent of potassium chloride, filtered off and dried at 50C. A dark powder is obtained which dissolves in water, with a blue-grey color.

In the form of the pentasodium salt, the dyestuff corresponds to the formula Example 1: 1 chromium complex (listed in Metal-free dycstufi (listed in sh d on No. terms of reaction components) terms of coupling components m 285 4-nitro-2-amino-1-hydroxybenzcne-S-sulphonic acid- 4-nitro-2-amino-1-hydroxybenzene 2-hydroxy- Black l-amino-8-hydroxynaphthalene-3,6d.isulphonic acid. naphthalene. 286". d "d0 D0. o Do. 4-nitro-2-amino-1-hydroxybenzene-Qhydroxy- Do.

naphthalene-fi-sulphonic acid. 289 do do Do. 290 do 4-nitr0-2-amino-143'droxybenzene l-hydroxy- Navy blue.

naphthalene-+5 phonic acid. 291 do 6-nitro-2amin0-1-hydroxybenzenc-4-sulphonic aeid Black.

2-hydroxynaphthalene. 292 .do 4-nitro-2-amino-1-hydroxybenzene l-acetylamino-7- D0.

hydroxynaphthalcne. 293 .do 6-nitro-l-amino-2-liydroxynaphthalcne-4-sulphonic acid Do.

2-hydroxynaphtlialene. 294 4-nitro-2-amino-1-hydroxybenzene-fi'sulphonic acid 4-nitro-2-amino-1-hydroxynaphthalcne-fi-sulphonic acid Do.

l-amino-B-hydroxy-naplithalene-4,fi-disulphonic acid. 2-hydroxynaphthaleno. 295 4-chloro-2-amino-1-hydroxybenzene-G-sulphonic acid 4-nitro-2-amino-1-l1ydroxybcnzene Blue-black.

1-amino-8-hydroxynaphthalcne-3,G-disulphonic acid. Z-hydroxynaphthalene. 296 do do Do. 297 d0 4-nitro-2-amino-1-hydroxybenzcne- 2-hydroxynaphthalene- Do.

G-sulphonic acid. 298 do 4-chloro-2-amino-1-hydroxybenzene Navy blue.

2-hydroxynaphthalene. 299 do 4-nitro-2aminoJ-hydroxybenzonel-acetylamino-S- Blue.

hydroxynaphthalenc-3,6-disulphonic acid. 300 do 4-nitro-2-amino-1-hydroxybcnzene-d-amino-8- Navy blue.

hydroxynaphthaleue-2,4-disu1phonic acid. 301 do 6-nitr0-1-amin0-2-hydroxynaphthalene-4-sulphonic acid Blue-black.

2-hydroxynaphthalene. 302" ..do 2-aminobenzene-l-carboxylic acid-S-sulphonic acid Grey-green.

. 1-phcnyl-3-methyl-5-pyrazolone. 303 4-n1tYO-Z-amiHO-LhYdIOXYb8I1Z6I1B45-S111Dh0niC acid- 6-nitro-1-amino-2-hydroxynaphthalene-4-sulphonic acid Black.

l-amino-8-hydroxynaphthalene-3,4-disulphonic acid. Z-hydroxynaphthalene. 304 4-chloro-2-aminol-hydroxybenzcne-G-sulphonic add- 4-chlor0-2 amino4-hydroxybenzcne 1-(4-sulphophenyl)- Violet. 1-amino-S-hydroxynaphthalenc-B,fi-disulphonic acid. 3-methyl-5-pyrazolonc. 305 4'methyl-2-amino-1-hydroxybenzene-G-sulphonic acid 4-chloro-2-amino-1-hydroxyben2ene Reddish-blue.

l-amino-8-hydroxynaphthalene-3,G-disulphonic acid. Z-hydroxynaphthalene-(S-sulphomc acid. 306 4 mtroQ-amino-l-hydroxybcnzenc-(S'sulphonic acid 5-nitro-2-amino-1-hydroxybenzene Black.

1- ino-S-hydroxynaphthalene-3,G-disulphonic acid. Z-hydroxynaphthalene-fi-sulphomc acid. 30 ..do 4-nitro-2-amino-1-hydroxybenzene7 D0 2-hydroxynaphthalene-8'sulphonic acid. 3 .do 4-nitro-2-amino-1-hydroxybenzene+1- D0.

hydroxynaphthalene-5-sulphonic acid. 9 do 6-nitro-4-chlore-1-hydroxybenzcue 1- hydroxynaphthalcnc-5-sulplionic acids.

.37.. EXAMPLE 310 In 180 ml of water are dissolved at 40C, 6 g of lamino-4-(4-aminophenyl-amino)-anthraquinone- 2,5,8-trisulphonic acid in the form of the sodium salt, the solution is adjusted to a pH of 8 and 2.2 g of 3,5- dichloro-l,2-isothiazole-4-carboxylic acid chloride are introduced in small portions at 4045'C. At the same time, a dilute sodium hydroxide solution is added dropwise in such a manner that a pH of 7.5-8.5 is maintained during the reaction. The mixture is further stirred at 4045C until the starting material has completely disappeared, filtered ofi with suction from excess isothiazole-carboxylic acid chloride and salted at 40C with a sufficient amount of solid sodium chloride to obtain an approximately 10 percent sodium chloride solution. The product is filtered off with suction, washed with a little sodium chloride solution and the resultant dyestuif of the formula IIIH:

is dried below 40C in a vacuum. About 8.5 g of the dyestuff are obtained in the form of blue-green needles.

The dyestuff dyes cotton by the methods customary for reactive dyestuffs in intense blue-green shades of good fastness to wet processing and light.

The l-amino-4-( 4 '-aminophenyl-amino anthraquinone-2,5,8-trisulphonic acid used as starting material is obtained as follows: 31.2 g of p-phenylenediamine are introduced under nitrogen into a solution of 62 g of l-amino-4-bromo-anthraquinone-2,5,8- trisulphonic acid sodium salt and 12 g of sodium carbonate and stirred with the addition of a CuCl paste at 40C, until disulphonated bromoaminoacid is no longer indicated. The solution is then mixed with dilute hydrochloric acid, the precipitated dyestuff is filtered off with suction, washed with dilute hydrochloric acid, treated in 300 ml of water with sufficient dilute sodium hydroxide solution that it just dissolves and that the dyestuff precipitates in the hot in the form of the sodium salt; the product is then washed and dried.

EXAMPLE 31 l The trisodium salt of the dyestuff obtained by sodaalkaline coupling from diazotized 4-chloro-2-amino-lhydroxybenzene-6-sulphonic acid and l-amino-8- hydroxynaphthalene-3,6-disulphonic acid, 62 parts, is mixed in 300 parts of water at 7080C and at a pH of 8-9 with 54.2 parts of the 1:1 chromium complex of the dyestuff from 6-nitrol -diazo-2-hydroxynaphthalene-4- sulphonic acid and 2-hydroxynaphthalene. A deep blue solution is formed after 10 minutes.

The mixed complex is acylated within about 15 minutes at 45C and a pH of4-6 with 21.6 parts of 3,5- dichloro-l,2-isothiazole-4-carboxylic acid chloride. The pH value is kept constant by the dropwise addition of a sodium carbonate solution. The acylated dyestuff is separated with percent of sodium chloride, filtered off with suction and dried at 50C, and has the formula A blue-black print of excellent fastness to light and washing is obtained on cotton by the known processes.

In the examples, those dyestuffs illustrated by formulas, which contain sulphonic acid groups, are generally given in the form of the sodium salts of the sulphonic acids. From these, the free acids (-SO H) or other salts can be produced in a known manner.

We claim:

1. Anthraquinone dyestuff of the formula wherein R is H, CH or Cl;

R' is H or CH and X and Y are Cl or Br.

2. The dyestuff of claim 1 having the formula 2.- Thqqysswffsf 9125. 21 har r hs a ms...

H 0 8 (l) N Hz SOQH l HOaS 0 

2. The dyestuff of claim 1 having the formula
 3. The dyestuff of claim 1 having the formula
 4. The dyestuff of claim 1 having the formula
 5. The dyestuff of claim 1 having the formula
 6. The dyestuff of claim 1 having the formula 